Polymers for use in fibers and nonwoven fabrics, articles thereof, and composites thereof

ABSTRACT

An ethylene/alpha-olefin interpolymer suitable for use in fibers and nonwovens having a density of from 0.911 to 0.939 g/cc, a Brookfield viscosity of less than or equal to 50,000 cP, and a molecular weight distribution (Mw,cc/Mn,cc) of 1.8 to 3.5, and articles thereof.

TECHNICAL FIELD

Embodiments of the present disclosure generally relate to ethylene/alpha-olefin interpolymers for use in fibers and nonwoven fabrics, and particularly, to ethylene/alpha-olefin interpolymers for use in meltblown fibers and meltblown nonwoven fabrics, articles thereof, and composites thereof.

BACKGROUND

Nonwoven fabrics (NW) are cloth-like materials that are manufactured from filaments which are brought together via different bonding techniques (e.g., spunbond or meltblown processes). These nonwoven fabrics may be used in hygiene and/or medical applications, such as, disposable absorbent articles, including diapers, wipes, feminine hygiene products, and adult incontinence products. In such applications, a spunbond meltblown spunbond (SMS) composite structure is becoming increasingly popular.

The spunbond layer was historically formed from polypropylene monocomponent fibers due to its mechanical performance One of the major drawbacks of polypropylene is the lack of softness. The softness can be addressed by the introduction of polyethylene (PE). Spunbond layers are increasingly being formed from bicomponent fibers having a polyethylene resin in the sheath and a polypropylene resin in the core. The polyethylene resin provides softness & improved haptics, a desirable feature in hygiene and/or medical applications, and the polypropylene provides strength and fiber spinnability.

Polypropylene resins are also typically used to form the meltblown layer because of its excellent processing characteristics in meltblown processes. However, in an SMS structure, the outer polyethylene sheath of the bicomponent fibers used to form the spunbond nonwoven is now bonded to a polypropylene meltblown layer. The melting temperature difference and incompatibility between polyethylene and polypropylene can create poor bonding between the layers since when the higher polypropylene melting temperature is used, the polyethylene can tend to ‘run away’ from the bonding point, and at the lower polyethylene melting temperature, the polypropylene does not melt properly. Thus, poor bonding strength in the SMS composite structure can result.

Accordingly, alternative resins may be desirable for use in meltblown nonwovens and in SMS composite structures that may exhibit improved bonding strength.

SUMMARY

Disclosed herein are ethylene/alpha-olefin interpolymers suitable for use in fibers and nonwovens. The interpolymers have a density of from 0.911 to 0.939 g/cc, a Brookfield viscosity of less than or equal to 50,000 cP, and a molecular weight distribution (M_(w,cc)/M_(n,cc)) of 1.8 to 3.5.

Also disclosed herein are meltblown nonwovens. The nonwovens comprise an ethylene/alpha-olefin interpolymer, wherein the ethylene/alpha-olefin interpolymer has a density of from 0.911 to 0.939 g/cc, a Brookfield viscosity of less than or equal to 50,000 cP, and a molecular weight distribution (M_(w,cc)/M_(n,cc)) of 1.8 to 3.5.

Further disclosed herein are composite structures. The composite structures comprise a meltblown nonwoven. The meltblown nonwoven comprises an ethylene/alpha-olefin interpolymer, wherein the ethylene/alpha-olefin interpolymer has a density of from 0.911 to 0.939 g/cc, a Brookfield viscosity of less than or equal to 50,000 cP, and a molecular weight distribution (M_(w,cc)/M_(n,cc)) of 1.8 to 3.5.

In one or more embodiments herein, the ethylene/alpha-olefin interpolymer has an M_(z,cc)/M_(n,cc) of less than 5.25. In one or more embodiments herein, the ethylene/alpha-olefin interpolymer has a weight fraction (w) of molecular weight greater than 10⁵ g/mole, based on the total weight of interpolymer, as determined by conventional gel permeation chromatography, of less than 2.5%. In one or more embodiments herein, the ethylene/alpha-olefin interpolymer has a comonomer distribution breadth index of greater than 50%.

In one or more embodiments herein, the composite structure further comprises one or more spunbond nonwovens. In one or more embodiments herein, the composite structure has an S_(a)M_(b)S_(c) configuration, wherein S is a spunbond nonwoven, M is a meltblown nonwoven as described herein, and a, b, and c are the number of layers and are independent integers ranging from 1 to 5. In one or more embodiments herein, the spunbond nonwoven is formed from bicomponent fibers having a sheath/core structure, wherein the sheath comprises polyethylene and the core comprises polypropylene. In one or more embodiments herein, the spunbond nonwoven is formed from monocomponent fibers, wherein the monocomponent fibers comprise polyethylene.

Additional features and advantages of the embodiments will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing and the following description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate the various embodiments described herein, and together with the description serve to explain the principles and operations of the claimed subject matter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 graphically depicts a chromatogram plot of the detector signal (V) versus retention volume (ml) and the proper baseline and integration limit sets for a sample that exhibits a clear separate antioxidant peak.

FIG. 2 graphically depicts a chromatogram plot of the detector signal (V) versus retention volume (ml) and the proper baseline and integration limits sets for a sample that shows continuity towards 100 polyethylene-equivalent molecular weight.

DETAILED DESCRIPTION

Reference will now be made in detail to embodiments of ethylene/alpha-olefin interpolymers, characteristics of which are illustrated in the accompanying drawings, which may be used to produce fibers or nonwovens, such as meltblown nonwoven fabrics for use in hygiene absorbent articles, such as, diapers, wipes, feminine hygiene, and adult incontinence products. It is noted, however, that this is merely an illustrative implementation of the embodiments disclosed herein. The embodiments are applicable to other technologies that are susceptible to similar problems as those discussed above. For example, the ethylene/alpha-olefin interpolymers may be used in meltblown nonwoven fabrics to produce face masks, surgical gowns, isolation gowns, surgical drapes and covers, surgical caps, tissues, bandages, and wound dressings are clearly within the purview of the present embodiments.

Ethylene/Alpha-Olefin Interpolymer

“Interpolymer” refers to a polymer prepared by the polymerization of at least two different types of monomers. The generic term “interpolymer” includes the term “copolymer” (which is usually employed to refer to a polymer prepared from two different monomers) as well as the term “terpolymer” (which is usually employed to refer to a polymer prepared from three different types of monomers). It also encompasses polymers made by polymerizing four or more types of monomers.

Ethylene/alpha-olefin interpolymer generally refers to polymers comprising ethylene and an alpha-olefin having 3 or more carbon atoms. In embodiments herein, the ethylene/alpha-olefin interpolymer comprises greater than 50 wt. % of the units derived from ethylene and less than 30 wt. % of the units derived from one or more alpha-olefin comonomers (based on the total amount of polymerizable monomers). All individual values and subranges of greater than 50 wt. % of the units derived from ethylene and less than 30 wt. % of the units derived from one or more alpha-olefin comonomers are included and disclosed herein. For example, in some embodiments, the ethylene/alpha-olefin interpolymer comprises (a) greater than or equal to 55%, for example, greater than or equal to 60%, greater than or equal to 65%, greater than or equal to 70%, greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 90%, greater than or equal to 92%, greater than or equal to 95%, greater than or equal to 97%, greater than or equal to 98%, greater than or equal to 99%, greater than or equal to 99.5%, from greater than 50% to 99%, from greater than 50% to 97%, from greater than 50% to 94%, from greater than 50% to 90%, from 70% to 99.5%, from 70% to 99%, from 70% to 97% from 70% to 94%, from 80% to 99.5%, from 80% to 99%, from 80% to 97%, from 80% to 94%, from 80% to 90%, from 85% to 99.5%, from 85% to 99%, from 85% to 97%, from 88% to 99.9%, 88% to 99.7%, from 88% to 99.5%, from 88% to 99%, from 88% to 98%, from 88% to 97%, from 88% to 95%, from 88% to 94%, from 90% to 99.9%, from 90% to 99.5% from 90% to 99%, from 90% to 97%, from 90% to 95%, from 93% to 99.9%, from 93% to 99.5% from 93% to 99%, or from 93% to 97%, by weight, of the units derived from ethylene; and (b) less than 30 percent, for example, less than 25 percent, or less than 20 percent, less than 18%, less than 15%, less than 12%, less than 10%, less than 8%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, from 0.1 to 20%, from 0.1 to 15%, 0.1 to 12%, 0.1 to 10%, 0.1 to 8%, 0.1 to 5%, 0.1 to 3%, 0.1 to 2%, 0.5 to 12%, 0.5 to 10%, 0.5 to 8%, 0.5 to 5%, 0.5 to 3%, 0.5 to 2.5%, 1 to 10%, 1 to 8%, 1 to 5%, 1 to 3%, 2 to 10%, 2 to 8%, 2 to 5%, 3.5 to 12%, 3.5 to 10%, 3.5 to 8%, 3.5% to 7%, or 4 to 12%, 4 to 10%, 4 to 8%, or 4 to 7%, by weight, of units derived from one or more a-olefin comonomers. The comonomer content may be measured using any suitable technique, such as techniques based on nuclear magnetic resonance (“NMR”) spectroscopy, and, for example, by 13C NMR analysis as described in U.S. Pat. No. 7,498,282, which is incorporated herein by reference.

Suitable alpha-olefin comonomers typically have no more than 20 carbon atoms. The one or more alpha-olefins may be selected from the group consisting of C3-C20 acetylenically unsaturated monomers and C4-C18 diolefins. For example, the alpha-olefin comonomers may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary alpha-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. The one or more alpha-olefin comonomers may, for example, be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or in the alternative, from the group consisting of 1-butene, 1-hexene and 1-octene, or in the alternative, from the group consisting of 1-hexene and 1-octene. In some embodiments, the ethylene/alpha-olefin interpolymer comprises greater than 0 wt. % and less than 30 wt. % of units derived from one or more of 1-octene, 1-hexene, or 1-butene comonomers.

In embodiments described herein, the ethylene/alpha-olefin interpolymer has a density of 0.911 to 0.939 grams/cubic centimeter (g/cc). All individual values and subranges of from 0.911 to 0.939 g/cc are included and disclosed herein. For example, in some embodiments, the polyethylene polymer has a density of 0.911 to 0.935 g/cc. In other embodiments, the polyethylene polymer has a density of 0.913 to 0.939 g/cc. In further embodiments, the polyethylene polymer has a density of 0.913 to 0.935 g/cc. Density may be measured according to ASTM D792.

In addition to the density, the ethylene/alpha-olefin interpolymer has a Brookfield viscosity of less than or equal to 50,000 centipoise (cP). All individual values and subranges of less than or equal to 50,000 cP are included and disclosed herein. For example, in some embodiments, the ethylene/alpha-olefin interpolymer has a Brookfield viscosity of less than or equal to 45,000 cP, less than or equal to 40,000 cP, or less than or equal to 35,000 cP. In other embodiments, ethylene/alpha-olefin interpolymer has a Brookfield viscosity of from 5,000 cP to 50,000 cP, from 5,000 cP to 45,000 cP, or 5,000 cP to 40,000 cP.

In addition to the density and Brookfield viscosity, the ethylene/alpha-olefin interpolymer has a molecular weight distribution (M_(w,cc)/M_(n,cc)) from 1.8 to 3.5. Molecular weight distribution can be described as the ratio of weight-average molecular weight (M_(w,cc)) to number average molecular weight (M_(n,cc)) (i.e., M_(w,cc)/M_(n,cc)), and can be measured by gel permeation chromatography (GPC) techniques. All individual values and subranges of from 1.8 to 3.5 are included and disclosed herein. For example, in some embodiments, the ethylene/alpha-olefin interpolymer has a molecular weight distribution (M_(w,cc)/M_(n,cc)) of from 1.9 to 3.5 or 2.0 to 3.5. In other embodiments, the ethylene/alpha-olefin interpolymer has a molecular weight distribution (MM_(w,cc)/M_(n,cc)) of from 1.8 to 3.0, 1.9 to 3.0, or 2.0 to 3.0. In further embodiments, the ethylene/alpha-olefin interpolymer has a molecular weight distribution (M_(w,cc)/M_(n,cc)) of from 1.8 to 2.8, 1.9 to 2.8, or 2.0 to 2.8.

In addition to the density, Brookfield viscosity, and molecular weight distribution, the ethylene/alpha-olefin interpolymer may have an M_(z,cc)/M_(n,cc) of less than 5.25. M_(z,cc) can be described as the z average molecular weight. All individual values and subranges of less than 5.25 are included and disclosed herein. For example, in some embodiments, the ethylene/alpha-olefin interpolymer has a M_(z,cc)/M_(n,cc) of less than 5.0, 4.5, 4.0, 3.8, or 3.5. In other embodiments, the ethylene/alpha-olefin interpolymer has a M_(z,cc)/M_(n,cc) of from 2.5 to 5.25, 2.5 to 5.0, 2.5 to 4.5, 2.5 to 4.0, 2.5 to 3.8, or from 2.5 to 3.5.

In addition to the density, Brookfield viscosity, molecular weight distribution, and M_(z,cc)/M_(n,cc), the ethylene/alpha-olefin interpolymer may have a weight fraction (w) of molecular weight greater than 10⁵ g/mole, based on the total weight of interpolymer, as determined by conventional gel permeation chromatography, of less than 2.5%. All individual values and subranges of less than 2.5% are included and disclosed herein. For example, in some embodiments, the ethylene/alpha-olefin interpolymer has a weight fraction (w) of molecular weight greater than 10⁵ g/mole, based on the total weight of interpolymer, as determined by conventional gel permeation chromatography, of less than 1.0%.

In addition to the density, Brookfield viscosity, molecular weight distribution, M_(z,cc)/M_(n,cc), and weight fraction (w) of molecular weight greater than 10⁵ g/mole, the ethylene/alpha-olefin interpolymer may have a comonomer distribution breadth index (CDBI) of greater than or equal to 50%. All individual values and subranges of greater than or equal to 50% are included and disclosed herein. For example, in some embodiments, the ethylene/alpha-olefin interpolymer has a CDBI of greater than or equal to 55%, greater than or equal to 60%, greater than or equal to 65%, greater than or equal to 70%, or greater than or equal to 75%. In other embodiments, the ethylene/alpha-olefin interpolymer has a CDBI ranging from 50% to 98%, 50% to 97%, 55% to 98%, 55% to 97%, 60% to 98%, 60% to 97%, 70% to 98%, 70% to 97%, 75% to 98%, or 75% to 97%. In further embodiments, the ethylene/alpha-olefin interpolymer has a CDBI ranging from 50% to 85%, 55% to 85%, 60% to 85%, 60% to 80%, 65% to 80%, or 70% to 80%.

In addition to the density, Brookfield viscosity, molecular weight distribution, M_(z,cc)/M_(n,cc), weight fraction (w) of molecular weight greater than 10⁵ g/mole, and CDBI, the ethylene/alpha-olefin interpolymer may have a highest DSC temperature crystallization peak, Tc, of from 80° C. to 110° C. All individual values and subranges of from 80° C. to 110° C. are included and disclosed herein. For example, in some embodiments, the ethylene/alpha-olefin interpolymer has a Tc of from 80° C. to 105° C., from 85° C. to 105° C., or from 90° C. to 105° C. In other embodiments, the ethylene/alpha-olefin interpolymer has a Tc of from 95° C. to 105° C. The highest DSC temperature crystallization peak is determined using the differential scanning calorimetry (DSC) method outlined below.

In addition to the density, Brookfield viscosity, molecular weight distribution, M_(z,cc)/M_(n,cc), weight fraction (w) of molecular weight greater than 10⁵ g/mole, CDBI, and Tc, the ethylene/alpha-olefin interpolymer may have a temperature differential between the highest DSC temperature melting peak (Tm) and the highest DSC temperature crystallization peak (Tc), ΔTm-Tc, of less than 16° C. All individual values and subranges of less than 16° C. are included and disclosed herein. For example, in some embodiments, the ethylene/alpha-olefin interpolymer may have a ΔTm-Tc of less than 15° C. In other embodiments, the ethylene/alpha-olefin interpolymer may have a ΔTm-Tc of less than 12° C. The highest DSC temperature melting peak (Tm) is determined using the differential scanning calorimetry (DSC) method outlined below.

In embodiments herein, the ethylene/alpha-olefin interpolymer may be prepared in a solution polymerization process using one or more conventional reactors e.g. loop reactors, isothermal reactors, plug flow reactors, and/or stirred tank reactors in parallel, series, and/or any combinations thereof in continuous or batch mode to produce olefin based polymers, e.g. ethylene polymers or propylene polymers. The solution phase polymerization process may occur in one or more well-stirred reactors, such as one or more loop reactors or one or more isothermal reactors, at a temperature in the range of from 100 to 300° C.; for example, from 120 to 190° C., and at pressures in the range of from 300 to 1,000 psig; for example, from 400 to 750 psig. The residence time in solution phase polymerization process is typically in the range of from 2 to 30 minutes; for example, from 5 to 20 minutes. Ethylene (monomer), solvent, hydrogen, one or more catalyst systems, and one or more comonomers are fed continuously to the reactor. Exemplary solvents include, but are not limited to, isoparaffins and naphthinics For example, such solvents are commercially available under the name ISOPAR E from ExxonMobil Chemical Co., Houston, Tex. or under the name SBP 100/140 from Shell Chemicals Europe. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits the reactor and enters a zone where it is contacted with a deactivating agent and, optionally, an acid scavenging agent (such as calcium stearate and the accompanying water of hydration) to stop the reaction and scavenge hydrogen chloride. In addition, various additives, such as antioxidants, can be added at this point. The stream then goes through another set of static mixing elements, such as Kenics helical static mixing elements, to evenly disperse the catalyst kill and additives. The effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from the other lower boiling reaction components. The stream then passes through a pressure let down control valve, which is responsible for maintaining the pressure of the reactor at a specified target. The stream then enters a multi-stage separation and devolatilization system where the polymer is removed from the solvent, hydrogen, and unreacted monomer and comonomer. Impurities are removed from the recycled, lower boiling reaction components before entering the reactor again. The separated and devolatilized polymer melt is pumped through a heat exchanger to lower the stream temperature to a temperature in the range of less than 200° C., for example less than 170° C., or in the range of from 50 to 110° C.; thereby producing a cooled polymer melt. Subsequently, the cooled polymer melt is pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transferred into a hopper. After validation of initial polymer properties, the solid polymer pellets are transferred to storage devices. The portions removed in the devolatilization step may be recycled or destroyed. For example, most of the solvent is recycled back to the reactor after passing through purification beds. This recycled solvent can still have unreacted co-monomer in it that is fortified with fresh co-monomer prior to re-entry to the reactor. This recycle solvent can also have some hydrogen which is then fortified with fresh hydrogen.

In some embodiments, the ethylene/alpha-olefin interpolymers may be prepared using a catalyst composition via a solution phase polymerization process in a loop reactor in accordance with the following procedure. All raw materials (ethylene, and one or more alpha-olefin comonomers, such as hexene or octene) and the process solvent (an isoparaffinic solvent, for example ISOPAR E) are purified with molecular sieves before introduction into the reaction environment. Hydrogen is supplied as a high purity grade and is not further purified. The reactor monomer feed (ethylene) stream is pressurized via a mechanical compressor to a pressure that is above the reaction pressure, e.g. 750 psig. The solvent and comonomer (one or more alpha-olefin comonomer, such as hexene or octene) feed is pressurized via a mechanical positive displacement pump to a pressure that is above the reaction pressure, e.g. 750 psig. The individual catalyst components can be manually batch diluted to specified component concentrations with purified solvent (ISOPAR E) and pressurized to a pressure that is above the reaction pressure, e.g. 750 psig. All reaction feed flows can be measured with mass flow meters and independently controlled with computer automated valve control systems.

The continuous solution polymerization reactor may consist of a liquid full, non-adiabatic, isothermal, circulating, loop. Independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds is possible. The combined solvent, monomer, comonomer and hydrogen feed is temperature controlled to anywhere between 5° C. to 50° C. and typically 40° C. by passing the feed stream through a heat exchanger. The fresh comonomer feed to the polymerization reactor is aligned to add comonomer to the recycle solvent. The total fresh feed to the polymerization reactor is injected into the reactor at, for example, two locations roughly with equal reactor volumes between each injection location. The fresh feed is controlled typically with each injector, for example, receiving half of the total fresh feed mass flow. The catalyst components are injected into the polymerization reactor through, for example, a specially designed injection inlet device and are combined into one mixed procatalyst/cocatalyst feed stream prior to injection into the reactor. The procatalyst component feed is computer controlled to maintain the reactor monomer concentration at a specified target. The cocatalyst component is fed based on calculated specified molar ratios to the procatalyst component Immediately following each fresh injection location (either feed or catalyst), the feed streams are mixed with the circulating polymerization reactor contents with static mixing elements, such as Kenics helical static mixing elements. The contents of the reactor are continuously circulated through heat exchangers responsible for removing much of the heat of reaction and with the temperature of the coolant side responsible for maintaining an isothermal reaction environment at the specified temperature. Circulation around the reactor loop can be provided by a screw pump. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits the reactor and enters a zone where it is contacted with a deactivating and, optionally, an acid scavenging agent (e.g., calcium stearate and the accompanying water of hydration) to stop the reaction and scavenge hydrogen chloride. In addition, various additives such as antioxidants can be added at this point. The stream then goes through another set of static mixing elements, such as Kenics helical static mixing elements to evenly disperse the catalyst kill and additives. The effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from the other lower boiling reaction components. The stream then passes through a pressure let down control valve, which is responsible for maintaining the pressure of the reactor at a specified target. The stream then enters a two stage separation and devolatilization system where the polymer is removed from the solvent, hydrogen, and unreacted monomer and comonomer. Impurities are removed from the recycled low boiling reaction components before entering the reactor again. The separated and devolatilized polymer melt is pumped through a heat exchanger to lower the stream temperature to a temperature in the range of less than 200° C., for example less than 170° C., or in the range of from 50 to 110° C.; thereby producing a cooled polymer melt. Subsequently, the cooled polymer melt is pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transferred into a hopper. After validation of initial polymer properties, the solid polymer pellets are transferred to storage devices. The portions removed in the devolatilization step may be recycled or destroyed. For example, most of the solvent is recycled back to the reactor after passing through purification beds. This recycled solvent can still have unreacted co-monomer in it that is fortified with fresh co-monomer prior to re-entry to the reactor. This recycle solvent can still have some hydrogen which is then fortified with fresh hydrogen.

In other embodiments, the ethylene/alpha-olefin interpolymer may be prepared using one or more catalyst systems suitable for polymerizing ethylene and one or more alpha-olefin comonomers via a solution phase polymerization process in two adiabatic stirred-tank reactors, linked together in series in accordance to the following procedure. The ethylene monomer and one or more alpha-olefin comonomers, and hydrogen are combined with a solvent, e.g. an isoparaffinic solvent, such as ISOPAR E. Impurities such as water, carbon dioxide, sulfurous compounds are removed from the feed streams, and the feed streams are cooled to temperature in the range of 5° C. to 60° C., for example, approximately 13° C., before entering the reactor. The majority, approximately from 85 to 90 percent, of the reaction may occur in the first adiabatic stirred-tank reactor. The mixing may be achieved via circulating the polymer/procatalyst/cocatalyst/solvent/ethylene/one or more alpha-olefin comonomers/hydrogen solution with one or more agitators equipped with mixing blades. The feed (ethylene/one or more alpha-olefin comonomers/solvent/hydrogen) may, for example, enter the reactor from the bottom and the procatalyst/cocatalyst may, for example, enter the reactor separately from the feed and also from the bottom. The first reactor temperature is in the range of from 120° C. to 190° C., for example, approximately 175° C., and the reactor pressure is in the range of from 400 psig to 1,000 psig, for example, approximately 500 psig. The temperature of the second reactor, in series with the first reactor, increases to a temperature in the range of from 175° C. to 210° C., for example, approximately 202° C. with approximately from 10 to 15 percent of the remaining reaction occurring and no additional catalyst or monomers are added. The average reactor residence time is in the range of from 2 to 30 minutes, for example, approximately 8 minutes per adiabatic stirred-tank reactor prior to termination post-reactor by a fluid specially designed for that purpose.

The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) exits the reactor and enters a zone where it is contacted with a deactivating and optionally an acid scavenging agent (e.g., calcium stearate and the accompanying water of hydration) to stop the reaction and scavenge hydrogen chloride. In addition, various additives such as antioxidants can be added at this point. The stream then goes through another set of static mixing elements, such as Kenics helical static mixing elements to evenly disperse the catalyst kill and additives. The effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components, and molten polymer) passes through a heat exchanger to raise the stream temperature in preparation for separation of the polymer from the other lower boiling reaction components. The stream then passes through a pressure let down control valve, which is responsible for maintaining the pressure of the reactor at a specified target. The stream then enters a two stage separation and devolatilization system where the polymer is removed from the solvent, hydrogen, and unreacted monomer and comonomer. Impurities are removed from the recycled lower boiling reaction components before entering the reactor again. The separated and devolatilized polymer melt is pumped through a heat exchanger to lower the stream temperature to a temperature in the range of less than 200° C., for example less than 170° C., or in the range of from 50 to 110° C.; thereby producing a cooled polymer melt. Subsequently, the cooled polymer melt is pumped through a die specially designed for underwater pelletization, cut into uniform solid pellets, dried, and transferred into a hopper. After validation of initial polymer properties, the solid polymer pellets are transferred to storage devices. The portions removed in the devolatilization step may be recycled or destroyed. For example, most of the solvent is recycled back to the reactor after passing through purification beds. This recycled solvent can still have unreacted co-monomer in it that is fortified with fresh co-monomer prior to re-entry to the reactor. This recycle solvent can still have some hydrogen which is then fortified with fresh hydrogen.

Fibers/Meltblown Nonwoven

The ethylene/alpha-olefin interpolymer may be used to form fibers and/or nonwovens, such as meltblown nonwovens. As used herein, “meltblown” refers to fibers formed by extruding a molten thermoplastic polymer composition through a plurality of fine, usually circular, die capillaries as molten threads or filaments into converging high velocity gas streams (e.g. air) which function to attenuate the threads or filaments to reduced diameters. Thereafter, the filaments or threads are carried by the high velocity gas streams and deposited on a collecting surface to form a nonwoven web of randomly dispersed meltblown fibers with average diameters generally smaller than 10 microns. The terms “nonwoven,” “nonwoven web,” and “nonwoven fabric” are used herein interchangeably. “Nonwoven” refers to a web or fabric having a structure of individual fibers or threads which are randomly interlaid, but not in an identifiable manner as is the case for a knitted fabric.

In embodiments herein, the meltblown nonwovens described herein may exhibit one or more of the following characteristics: at 100 gsm, a 5% improvement in air permeability in comparison to a 100 gsm meltblown nonwoven formed from an ethylene/alpha-olefin interpolymer having a Brookfield viscosity greater than 50,000 cP, a density ranging from 0.911 g/cc to 0.939 g/cc, and a molecular weight distribution (M_(w,cc)/M_(n,cc)) ranging from 1.8 to 3.5, and/or at 25 gsm, a 5% improvement in hydrohead failure pressure in comparison to a meltblown nonwoven formed from an ethylene/alpha-olefin interpolymer having a Brookfield viscosity greater than 50,000 cP, a density ranging from 0.911 g/cc to 0.939 g/cc, and a molecular weight distribution (M_(w,cc)/M_(n,cc)) ranging from 1.8 to 3.5. % Improvement is calculated as follows:

${\%\mspace{14mu}{Improvement}} = {\frac{\left( {{{Inventive}\mspace{14mu}{value}} - {{Comparative}\mspace{14mu}{value}}} \right)}{{Comparative}\mspace{14mu}{value}} \times 100\%}$

The meltblown nonwoven may be used in a composite structure. The composite structure may further comprise one or more spunbond nonwovens. As used herein, “spunbond” refers to fibers formed by extruding a molten thermoplastic polymer composition as filaments through a plurality of fine, usually circular, die capillaries of a spinneret with the diameter of the extruded filaments then being rapidly reduced and thereafter depositing the filaments onto a collecting surface to form a web or fabric of randomly dispersed spunbond fibers with average diameters generally between about 7 and about 30 microns. The spunbond fibers may be bicomponent or monocomponent fibers. The monocomponent fibers comprise polyethylene. The bicomponent fibers may have a sheath/core structure where the sheath comprises polyethylene and the core comprises polypropylene. Of course, other configurations of bicomponent fibers may be used, such as, a side by side arrangement, a pie arrangement, or an “islands-in-the sea” arrangement.

In some embodiments, the composite has a S_(a)M_(b)S_(c) configuration, wherein S is a spunbond nonwoven, M is the meltblown nonwoven as described herein, and a, b, and c are the number of layers, and are independent integers ranging from 1 to 5. For example, the composite may have a SMS (where a=1, b=1, and c=1), SMMS (where a=1, b=2, and c=1), SSMSS (where a=2, b=1, and c=2), SMMMS (where a=1, b=3, and c=1), SMMSS (where a=1, b=3, and c=2), or other configurations, as “a,”, “b,” and “c” are independent of each other.

In embodiments herein, a meltblown nonwoven comprises an ethylene/alpha-olefin interpolymer as described herein. The meltblown nonwovens described herein may be a monolayer structure or a composite structure, such as a SMS composite structure. In embodiments herein, the SMS composite structure may exhibit one or more of the following characteristics: at least a 5% improvement in MD peak tensile strength as compared to a SMS composite structure wherein the meltblown nonwoven is formed from an ethylene/alpha-olefin interpolymer having a Brookfield viscosity greater than 50,000 cP, a density ranging from 0.911 g/cc to 0.939 g/cc, and a molecular weight distribution (M_(w,cc)/M_(n,cc)) ranging from 1.8 to 3.5; at least a 5% improvement in CD peak tensile strength as compared to a SMS composite structure wherein the meltblown nonwoven is formed from an ethylene/alpha-olefin interpolymer having a Brookfield viscosity greater than 50,000 cP, a density ranging from 0.911 g/cc to 0.939 g/cc, and a molecular weight distribution (M_(w,cc)/M_(n,cc)) ranging from 1.8 to 3.5; an MD elongation at break that is at least 5% higher than an MD elongation at break for a SMS composite structure wherein the meltblown nonwoven is formed from an ethylene/alpha-olefin interpolymer having a Brookfield viscosity greater than 50,000 cP, a density ranging from 0.911 g/cc to 0.939 g/cc, and a molecular weight distribution (M_(w,cc)/M_(n,cc)) ranging from 1.8 to 3.5; and/or an CD elongation at break that is at least 5% higher than an CD elongation at break for a SMS composite structure wherein the meltblown nonwoven is formed from an ethylene/alpha-olefin interpolymer having a Brookfield viscosity greater than 50,000 cP, a density ranging from 0.911 g/cc to 0.939 g/cc, and a molecular weight distribution (M_(w,cc)/M_(n,cc)) ranging from 1.8 to 3.5. The % improvement is calculated the same as above. The % higher value is calculated as [inventive value]−[comparative value].

In embodiments herein, the SMS composite structure may exhibit one or more of the following characteristics: at least a 10% (or alternatively, at least a 15%, 20%, 25%, 30%, 35%, or 40%) improvement in MD peak tensile strength as compared to a SMS composite structure wherein the meltblown nonwoven is formed from a polypropylene homopolymer having a 0.900 g/cc density and melt flow ratio (at 230° C., 2.16 kg) of 1200 g/10 min; at least a 10% (or alternatively, at least a 15%, 20%, 25%, 30%, 35%, or 40%) improvement in CD peak tensile strength as compared to a SMS composite structure wherein the meltblown nonwoven is formed from a polypropylene homopolymer having a 0.900 g/cc density and melt flow ratio (at 230° C., 2.16 kg) of 1200 g/10 min; an MD elongation at break that is at least 10% (or alternatively, at least a 15%, 20%, 25%, 30%, 35%, or 40%) higher than an MD elongation at break for a SMS composite structure wherein the meltblown nonwoven is formed from a polypropylene homopolymer having a 0.900 g/cc density and melt flow ratio (at 230° C., 2.16 kg) of 1200 g/10 min; and/or an CD elongation at break that is at least 10% (or alternatively, at least a 15%, 20%, 25%, 30%, 35%, or 40%) higher than a CD elongation at break for a SMS composite structure wherein the meltblown nonwoven is formed from a polypropylene homopolymer having a 0.900 g/cc density and melt flow ratio (at 230° C., 2.16 kg) of 1200 g/10 min

Test Methods Density

Density is measured in accordance with ASTM D-792, and expressed in grams/cubic centimeter (g/cc).

Brookfield Viscosity

Brookfield Viscosity is measured with a DV-II Pro Extra Viscometer. The instrument uses the Rheocalc V3.3 software which gives a great control and precision of the viscometer. 8 grams of sample is used when using the SC4-31 spindle size. Test temperature is 350 F° . Adequate spindle speed is applied so that the torque is between 40% to 70% level. Viscosity data is recorded after 20 minutes when a stable viscosity reading is obtained.

Conventional GPC

Conventional GPC is obtained by high temperature gel permeation chromatography (GPC) equipment (PolymerChar, Spain). The IRS detector (“measurement channel”) is used as a concentration detector. GPCOne software (PolymerChar, Spain) is used to calculate the z-average (Mz), weight-average (Mw), and number-average (Mn) molecular weight of the polymer and to determine the MWD (=Mw/Mn). The method uses three 10 micron PL gel mixed B columns (Agilent Technologies, column dimension 100 X 7.6 mm) or four 20 micron PL gel mixed A columns (Agilent Technologies, column dimension 100×7.6 mm) operating at a system temperature of 150° C. Samples are prepared at a 2 mg/mL concentration in 1,2,4-trichlorobenzene solvent containing 200 part per million of antioxidant butylated hydroxytoluene (BHT) for 3 hours at 160° C. with a gentle shaking by autosampler (PolymerChar, Spain). The flow rate is 1.0 mL/min, the injection size is 200 microliters. GPCOne software is used to calculate the plate count. The chromatographic system must have a minimum of 22,000 plates.

The GPC column set is calibrated by running at least 20 narrow molecular weight distribution polystyrene standards. The calibration uses a third order fit for the system with three 10 micron PL gel mixed B columns or a fifth order fit for the system with four 20 micron PL gel mixed A columns The molecular weight (MW) of the standards range from 580 g/mol to 8,400,000 g/mol, and the standards are contained in 6 “cocktail” mixtures. Each standard mixture has approximately a decade of separation between individual molecular weights. The standard mixtures are purchased from Agilent Technologies. The polystyrene standards are prepared at “0.025 g in 50 mL of solvent” for molecular weights equal to, or greater than, 1,000,000 g/mol, and at “0.05 g in 50 mL of solvent” for molecular weights less than 1,000,000 g/mol. The polystyrene standards are dissolved at 80° C., with gentle agitation, for 30 minutes. The narrow standards mixtures are run first, and in order of decreasing highest molecular weight component, to minimize degradation. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using Equation (1) (as described in Williams and Ward, J. Polym. Sci., Polym. Letters, 6, 621 (1968)): MW _(PE) =A×(MW _(PS))^(B)   (Eq. 1) where MW is the molecular weight of polyethylene (PE) or polystyrene (PS) as marked, and B is equal to 1.0. It is known to those of ordinary skill in the art that A may be in a range of about 0.38 to about 0.44 such that the A value yields 52,000 MWPE for Standard Reference Materials (SRM) 1475a. Use of this polyethylene calibration method to obtain molecular weight values, such as the molecular weight distribution (MWD or Mw/Mn), and related statistics, is defined here as the modified method of Williams and Ward. The number-average molecular weight, the weight-average molecular weight, and the z-average molecular weight are calculated from the following equations. M _(n,cc) =Σw _(i)/Σ(w _(i) /M _(cc,i))   (Eq. 2) M _(w,cc) =Σw _(i) M _(cc,i)   (Eq. 3) M_(z,cc)=Σ(w _(i) M _(cc,i) ²)/Σ(w _(i) M _(cc,i))   (Eq. 4) where M_(n,cc), M_(w,cc) and M_(z,cc) (in g/mole) are the number-, weight-, and z-average molecular weight obtained from the conventional calibration, respectively. w_(i) is the weight fraction of the polyethylene molecules eluted at retention volume V_(i). M_(cc,i) is the molecular weight (in g/mole) of the polyethylene molecules eluted at retention volume V_(i) obtained using the conventional calibration (see Equation (1)).

The chromatographic peaks should be set to include area marking a significant visible departure from baseline when the chromatogram is viewed at 20 percent peak height. The baseline should not be integrated to less than 100 polyethylene-equivalent molecular weight and care must be used to account for anti-oxidant mismatch from the prepared sample and the chromatographic mobile phase. Referring to FIG. 1, depicted is the proper baseline and integration limit sets for a sample that exhibits a clear separate anti-oxidant peak.

Use of a decane flow rate marker is shown in the IR5 chromatogram (see FIGS. 1 and 2). At no point should the baseline (response) Y-value difference between the start and the end of the baseline be greater than 3 percent of the integrated peak height of the chromatogram. In such a case, the chromatographic sample must be handled through proper matching of the sample and mobile phase antioxidant.

Referring to FIG. 2, depicted is the proper baseline and integration limits sets for a sample that shows continuity towards 100 polyethylene-equivalent molecular weight. At no point should the end integration limit be set lower than 100 polyethylene-equivalent molecular weight.

w (wt. fraction greater than 10⁵ g/mole) is calculated according the MWD curve (wi versus log Mcc, i) obtained from GPCOne software according to Equation (5)

$\begin{matrix} {w = {\int\limits_{{\log\; M_{{cc},i}} = 5}^{{\log\; M_{{cc},i}} = 7}{w_{i}d\;\log\; M_{{cc},i}\mspace{11mu}\text{/}{\int\limits_{{\log\; M_{{cc},i}} = 2}^{{\log\; M_{{cc},i}} = 7}{w_{i}d\;\log\; M_{{cc},i}}}}}} & \left( {{Eq}.\mspace{11mu} 5} \right) \end{matrix}$

Triple Detector Gel Permeation Chromatography (TDGPC)—Light Scattering GPC

For the GPC techniques used herein (Light Scattering GPC), a Triple Detector Gel Permeation Chromatography (3D-GPC or TDGPC) system is used. This system consists of a PolymerChar (Valencia, Spain) GPC-IR High Temperature Chromatograph, equipped with a Precision Detectors (Now Agilent Technologies) 2-angle laser light scattering (LS) detector Model 2040, an IRS infra-red detector, and 4-capillary viscometer detector from PolymerChar. Data collection and data processing are performed using PolymerChar “Instrument Control” and GPCOne software. The system is also equipped with an on-line solvent degassing device from Agilent Technologies (CA, USA). GPCOne software is used to calculate the plate count. The chromatographic system must have a minimum of 22,000 plates.

The eluent from the GPC column set flows through each detector arranged in series, in the following order: IRS detector, LS detector, then the Viscometer detector. The systematic approach for the determination of multi-detector offsets is performed in a manner consistent with that published by Balke, Mourey, et al. (Mourey and Balke, Chromatography Polym., Chapter 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym., Chapter 13, (1992)), optimizing triple detector log (MW and intrinsic viscosity) results from using a broad polyethylene standard, as outlined below.

Four 20-micron mixed-pore-size packing (“Mixed A”, Agilent Technologies) are used for the separation. The PolymerChar Autosampler oven compartment is operated at 160° C. with low speed shaking for 3 hours, and the column compartment is operated at 150° C. The samples are prepared at a concentration of “2 milligrams per milliliter.” The chromatographic solvent and the sample preparation solvent is 1,2,4-trichlorobenzene (TCB) containing “200 ppm of 2,6-di-tert-butyl-4methylphenol (BHT).” The solvent is sparged with nitrogen. The injection volume is 200 microliters. The flow rate through the GPC is set at 1 ml/minute.

For the LS GPC, the Precision Detector PDI2040 detector Model 2040 15° angle is used. The molecular weight data is obtained in a manner consistent with that published by Zimm (Zimm, B. H., J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, N.Y. (1987)), which are incorporated herein by reference. The overall injected concentration, used in the determination of the molecular weight, is obtained from the mass detector (IRS) area, and the mass detector constant, derived from a suitable linear polyethylene homopolymer, or one of the polyethylene standards of known weight-average molecular weight. The calculated molecular weights are obtained using a light scattering constant, derived from one or more of the polyethylene standards mentioned below, and a refractive index concentration coefficient, dn/dc, of 0.104. Generally, the mass detector response and the light scattering constant should be determined from a linear standard with a molecular weight in excess of about 50,000 g/mole. The viscometer calibration can be accomplished using the methods described by the manufacturer, or, alternatively, by using the published values of suitable linear standards, such as Standard Reference Materials (SRM) 1475a (available from National Institute of Standards and Technology (NIST)). The chromatographic concentrations are assumed low enough to eliminate addressing 2nd viral coefficient effects (concentration effects on molecular weight).

With 3D-GPC, absolute weight-average molecular weight (“M_(w,abs)”) and absolute z-average molecular weight (“M_(z,abs)”) is determined using Equations (6) and (7) below, wherein the M_(w,abs) is obtained using the “peak area” method (after detector calibration relating areas to mass and mass-molecular weight product) for higher accuracy and precision. The “LS.Area” and the “Concentration.Area” are generated by the chromatograph/detectors combination.

$\begin{matrix} {M_{w,{abs}} = {\frac{\sum{C_{i}M_{{abs},i}}}{\sum C_{i}} = {\frac{\sum{LS}_{i}}{\sum C_{i}} = \frac{{LS} \cdot {Area}}{{Concentration} \cdot {Area}}}}} & \left( {{Eq}.\mspace{11mu} 6} \right) \\ {M_{z,{abs}} = {\sum{\left( {w_{i}M_{{abs},i}^{2}} \right)\text{/}{\sum\left( {w_{i}M_{{abs},i}} \right)}}}} & \left( {{Eq}.\mspace{11mu} 7} \right) \end{matrix}$ where C_(i) is the concentration of the polyethylene molecules in the eluent at the retention volume V_(i), M_(abs,i) is the absolute molecular weight of the polyethylene molecules at the retention volume V_(i), LS_(i) is the response of the light scattering detector at the retention volume V₁, ΣLS_(i) (LS.Area) is the total response of the light scattering, and the ΣCi (Concentration.Area) is the total concentration.

The weight-average molecular weight by light scattering (LS) using Equation (6) is commonly referred to as “absolute weight-average molecular weight” or “M_(w, abs).” The M_(n,cc), M_(w,cc), and M_(z,cc) from Equation (2, 3, 4) use conventional GPC molecular weight calibration curve (“conventional calibration”) and M_(w,cc) is often referred to as “polymer chain backbone molecular weight,” “conventional weight-average molecular weight,” and “M_(w,cc)”.

Differential Scanning Calorimetry (DSC)

DSC was used to measure the melting and crystallization behavior of a polymer over a wide range of temperatures. For example, the TA Instruments Q1000 DSC, equipped with an RCS (refrigerated cooling system) and an autosampler was used to perform this analysis. During testing, a nitrogen purge gas flow of 50 ml/min was used. Each sample was melt pressed into a thin film at about 175° C.; the melted sample was then air-cooled to room temperature (approx. 25° C.). The film sample was formed by pressing a “0.1 to 0.2 gram” sample at 175° C. at 1,500 psi, and 30 seconds, to form a “0.1 to 0.2 mil thick” film. A 3-10 mg, 6 mm diameter specimen was extracted from the cooled polymer, weighed, placed in a light aluminum pan (ca 50 mg), and crimped shut. Analysis was then performed to determine its thermal properties.

The thermal behavior of the sample was determined by ramping the sample temperature up and down to create a heat flow versus temperature profile. First, the sample was rapidly heated to 180° C., and held isothermal for five minutes, in order to remove its thermal history. Next, the sample was cooled to −40° C., at a 10° C./minute cooling rate, and held isothermal at −40° C. for five minutes. The sample was then heated to 150° C. (this is the “second heat” ramp) at a 10° C./minute heating rate. The cooling and second heating curves were recorded. The cool curve was analyzed by setting baseline endpoints from the beginning of crystallization to −20° C. The heat curve was analyzed by setting baseline endpoints from −20° C. to the end of melt. The values determined were highest peak melting temperature (T_(m)), highest peak crystallization temperature (T_(c)), heat of fusion (H_(f)) (in Joules per gram), and the calculated % crystallinity for polyethylene samples using: % Crystallinity=((H_(f))/(292 J/g))×100. The heat of fusion (H_(f)) and the highest peak melting temperature were reported from the second heat curve. The highest peak crystallization temperature is determined from the cooling curve.

Crystallization Elution Fractionation (CEF) Method

Comonomer distribution analysis, also commonly called short chain branching distribution (SCBD), is measured with Crystallization Elution Fractionation (CEF) (PolymerChar, Spain) (Monrabal et al, Macromol. Symp. 257, 71-79 (2007), which is incorporated herein by reference) equipped with IR-4 detector (PolymerChar, Spain) and two angle light scattering detector Model 2040 (Precision Detectors, currently Agilent Technologies). IR-4 or IR-5 detector is used. A 10 or 20 micron guard column of 50×4.6 mm (PolymerLab, currently Agilent Technologies) is installed just before the IR-4 detector or IR-5 detector in the detector oven. Ortho-dichlorobenzene (ODCB, 99% anhydrous grade) and 2,5-di-tert-butyl-4-methylphenol (“BHT”, catalogue number B1378-500G, batch number 098K0686) from Sigma-Aldrich are obtained. ODCB is distilled before use. Silica gel 40 (particle size 0.2-0.5 mm, catalogue number 10181-3) from EMD Chemicals is also obtained. The silica gel is dried in a vacuum oven at 160° C. for about two hours before use. Eight hundred milligrams of BHT and five grams of the silica gel are added to two liters of ODCB. ODCB can be also dried by passing through a column or columns packed with silica gel. For the CEF instrument equipped with an autosampler with N2 purging capability, Silica gel 40 is packed into two 300×7.5 mm GPC size stainless steel columns and the Silica gel 40 columns are installed at the inlet of the pump of the CEF instrument to dry ODCB; and no BHT is added to the mobile phase. This “ODCB containing BHT and silica gel” or ODCB dried with silica gel 40 is now referred to as “ODCB.” This ODCB is sparged with dried nitrogen (N2) for one hour before use. Dried nitrogen is such that is obtained by passing nitrogen at <90 psig over CaCO₃ and 5 Å molecular sieves. The resulting nitrogen should have a dew point of approximately −73° C. Sample preparation is done with autosampler at 4 mg/ml (unless otherwise specified) under shaking at 160° C. for 2 hours. The injection volume is 300 μl. The temperature profile of CEF is: crystallization at 3° C./min from 110° C. to 30° C., the thermal equilibrium at 30° C. for 5 minutes (including Soluble Fraction Elution Time being set as 2 minutes), elution at 3° C./min from 30° C. to 140° C. The flow rate during crystallization is 0.052 ml/min The flow rate during cooling step is 0.052 mL/min The flow rate during elution is 0.50 ml/min. The data is collected at one data point/second. The CEF column is packed with glass beads at 125 μm±6% (MO-SCI Specialty Products) with ⅛ inch stainless tubing according to U.S. Pat. No. 8,372,931, which is incorporated herein by reference. The column outside diameter (OD) is ⅛ inch. The critical parameters needed to duplicate the method include the column internal diameter (ID), and column length (L). The choice of ID and L must be such that when packed with the 125pm diameter glass beads, the liquid internal volume is 2.1 to 2.3 mL. If L is 152 cm, then ID must be 0.206 cm and the wall thickness must be 0.056cm. Different values for L and ID can be used, as long as the glass bead diameter is 125 μm and the internal liquid volume is between 2.1 and 2.3 mL. Column temperature calibration is performed by using a mixture of NIST Standard Reference Material Linear polyethylene 1475a (1.0 mg/ml) and Eicosane (2mg/ml) in ODCB. CEF temperature calibration consists of four steps: (1) Calculating the delay volume defined as the temperature offset between the measured peak elution temperature of Eicosane minus 30.00° C.; (2) Subtracting the temperature offset of the elution temperature from CEF raw temperature data. It is noted that this temperature offset is a function of experimental conditions, such as elution temperature, elution flow rate, etc.; (3) Creating a linear calibration line transforming the elution temperature across a range of 30.00° C. and 140.00° C. so that NIST linear polyethylene 1475a has a peak temperature at 101.0° C., and Eicosane has a peak temperature of 30.0° C.; (4) For the soluble fraction measured isothermally at 30° C., the elution temperature is extrapolated linearly by using the elution heating rate of 3° C./min. The reported elution peak temperatures are obtained such that the observed comonomer content calibration curve agrees with those previously reported in U.S. Pat. No. 8,372,931, which is incorporated herein by reference. CEF data is processed by GPCOne software (PolymerChar, Spain).

Comonomer Distribution Breadth Index (CDBI)

The CDBI is defined as the weight percent of the polymer molecules having a co-monomer content within 50 percent of the median total molar co-monomer content (as reported in WO 93/03093, which is incorporated herein by reference). The CDBI of polyolefins can be conveniently calculated from the short chain branching distribution (SCBD) data obtained from the techniques known in the art, such as, for example, temperature rising elution fractionation (“TREF”) as described, for example, by Wild, et al., Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, 441 (1982); L. D. Cady, “The Role of Comonomer Type and Distribution in LLDPE Product Performance,” SPE Regional Technical Conference, Quaker Square Hilton, Akron, Ohio, 107-119 (Oct. 1-2, 1985); or in U.S. Pat. Nos. 4,798,081 (Hazlitt, et al.) and U.S. Pat. No. 5,008,204 (Stehling), all of which are incorporated herein by reference.

Herein, CDBI is calculated according to the following steps with the SCBD measured by CEF:

(A) Obtain a weight fraction at each temperature (T) (wT(T)) from 20.0° C. to 119.0° C. with a temperature step increase of 0.200° C. from CEF according to the equation ∫_(20.0) ^(119.9) wT(T)dT=1.00

(B) Calculate the median temperature (T_(median)) at cumulative weight fraction of 0.500 (50%) including soluble fraction. The cumulative weight fraction for the entire elution temperature range (generally between 20.0 to 120.0° C.) is normalized as 1.00

(C) Calculate the corresponding median total comonomer content in mole % (C_(median)) at the median temperature (T_(median)) by using comonomer content calibration versus elution temperature

(D) Construct a comonomer content calibration curve by using a series of reference materials (ethylene-octene copolymers) with known amount of comonomer content, i.e., eleven reference materials with narrow comonomer distribution (mono-modal comonomer distribution in CEF from 35.0 to 119.0° C.) with weight-average Mw (by conventional GPC) of 35,000 to 115,000 (measured via conventional GPC) at a comonomer content ranging from 0.0 mole % to 7.0 mole % are analyzed with CEF at the same experimental conditions specified in CEF experimental sections. The comonomer content of the reference materials is determined using 13C NMR analysis in accordance with techniques described, for example, in U.S. Pat. No. 5,292,845 (Kawasaki, et al.) and by J. C. Randall in Rev. Macromol. Chem. Phys., C29, 201-317, which are incorporated herein by reference.

(E) Calculate comonomer content calibration by using the peak temperature (T_(p)) of each reference material and its comonomer content; The calibration is calculated from each reference material as shown in the following equation, wherein: R² is the correlation constant;

${\ln\left( {1 - {comonomercontent}} \right)} = {{- \frac{207.26}{273.12 + r}} + 0.5533}$ R² = 0.997

(F) Calculate CDBI as the total weight percentage with a comonomer content ranging from 0.5*C_(median) to 1.5*C_(median). If the density of the polymer is above 0.94, CDBI is thus defined as 100% (see WO1993003093 A1, which is incorporated herein by reference)

Peak Tensile Strength/Elongation at Break

The following procedures are used to generate tensile testing data for nonwoven fabrics of the present invention. Basis weight may be determined by measuring the weight of a known area of fabric. For example, basis weight in g/m² may be determined according to ASTM D 3776.

Peak tensile strength and elongation at break are measured according to ASTM D5035. A strip of specimen (1 inch wide by 6 inch long) is cut from the nonwoven fabric and tested with a 3 inch gauge length (grip separation). The length direction of the specimen is the machine direction (MD) to get the tensile properties in MD or the cross direction (CD) to get the tensile properties in CD. Testing speed is 12 inches/min

Peak tensile strength and elongation at break of the nonwoven materials are determined using the following procedures. Peak tensile strength is the maximum or peak force applied to a material prior to rupture. Materials that are brittle usually rupture at the maximum force. Materials that are ductile usually experience a maximum force before rupturing, A high precision electronic test instrument is used that measures the elongation at break and peak tensile strength of materials while pulling forces are applied to the material. The force which is exerted on the specimen is read directly from the testing machine or graphs obtained during the test procedure, For each sample at least 5 specimens were tested and the average was calculated and used for the peak tensile strength observed for the sample.

Elongation at Break is the deformation in the direction of load caused by a tensile force. Elongation is expressed as a ratio of the length of the stretched material as a percentage to the length of the unstretched material. Elongation at break is determined at the point where the stretched material breaks. The apparent elongation is determined by the increase in length from the start of the force-extension curve to a point corresponding with the breaking force. The apparent elongation is calculated as the percentage increase in length based on the gage length (L₀).

${{Elongation}\mspace{14mu}(\%)} = {\frac{L_{break} - L_{o}}{L_{o}} \times 100\%}$

Air Permeability

Air permeability is tested with a FX 3300 Air Permeability Tester III manufactured by TexTest Instruments, and expressed in cubic feet per minute. Test pressure is 125 Pa and test area is 20 cm².

Hydrohead Failure Pressure

Hydrohead failure pressure test is performed according to AATCC 127 with a TexTest FX3000 hydrostatic head tester, and expressed in millibar (mbar). The test area is 100 cm² and the gradient is 60 mbar/min. An average value of five specimens is reported.

Hydrohead Failure Pressure (ISO)

Hydrohead failure pressure test is performed according to ISO 811 with a TexTest FX3000 hydrostatic head tester, and expressed in millibar (mbar). The testing area is 100 cm² with a gradient of 60 mbar/min. An average value of five specimens is reported.

Hand Feel

Handle-O-Meter stiffness of the nonwoven samples was performed on a Thwing-Albert Handle-O-Meter, Model 211-300, according to EDANA test method WSP 90.3.0 (05), and expressed in grams. The Handle-O-Meter is a commercially available apparatus from the Thwing-Albert Company. The Handle-O-Meter measures “handle” or “hand feel”which takes into account the combined effects of stiffness or bendability and surface friction of sheeted materials such as nonwovens, films, and laminates. Conditions for evaluation: a single ply 100 mm by 100 mm sample is evaluated using a 100 gm beam assembly and a 5 mm slot width. The fabric is pushed into the slot by the beam and the “handle” or “hand feel” is the resistance that the fabric exerts on the beam as it is pushed into the slot. Lower “handle” or “hand feel” values indicates softer and more drapeable fabrics.

EXAMPLES Comparative Polymers 1-4

Comparative polymer 1 (Comp. 1) is a polypropylene homopolymer (Metocene MF650W), available from LyondellBasell Industries N.V. (Houston, Tex.), having a density according to ASTM D792, of 0.90 g/cc and a melt flow rate, according to ASTM D1238, of 500 g/10 min at 230° C., 2.16 kg. Additional characteristics of the polymer are provided in the tables below.

Comparative polymer 2 (Comp. 2) is a polypropylene homopolymer (Metocene MF650X), available from LyondellBasell Industries N.V. (Houston, Tex.), having a density according to ASTM D792, of 0.90 g/cc and a melt flow rate, according to ASTM D1238, of 1200 g/10 min at 230° C., 2.16 kg. Additional characteristics of the polymer are provided in the tables below.

Comparative polymer 3 (Comp. 3) is a polypropylene homopolymer (Metocene MF650Y), available from LyondellBasell Industries N.V. (Houston, Tex.), having a density according to ASTM D792, of 0.90 g/cc and a melt flow rate, according to ASTM D1238, of 1800 g/10 min at 230° C., 2.16 kg. Additional characteristics of the polymer are provided in the tables below.

Comparative polymer 4 (Comp. 4) is an ethylene/alpha-olefin interpolymer, available as DNDA 1082 NT7 from The Dow Chemical Company (Midland, Mich.). Additional characteristics of the polymer are provided in the tables below.

Production of Inventive Polymers 1-5

The inventive ethylene/alpha-olefin interpolymers 1-5 were prepared according to the following process and based on the reaction conditions reported in Tables 1 and 2.

All raw materials (monomer and comonomer) and the process solvent (a narrow boiling range high-purity isoparaffinic solvent, Isopar-E) are purified with molecular sieves before introduction into the reaction environment. Hydrogen is supplied pressurized as a high purity grade and is not further purified. The reactor monomer feed stream is pressurized via a mechanical compressor to above reaction pressure. The solvent and comonomer feed is pressurized via a pump to above reaction pressure. The individual catalyst components are manually batch diluted to specified component concentrations with purified solvent and pressured to above reaction pressure. All reaction feed flows are measured with mass flow meters and independently controlled with computer automated valve control systems.

The continuous solution polymerization reactor consists of a liquid full, non-adiabatic, isothermal, circulating, loop reactor which mimics a continuously stirred tank reactor (CSTR) with heat removal. Independent control of all fresh solvent, monomer, comonomer, hydrogen, and catalyst component feeds is possible. The total fresh feed stream to the reactor (solvent, monomer, comonomer, and hydrogen) is temperature controlled by passing the feed stream through a heat exchanger. The total fresh feed to the polymerization reactor is injected into the reactor at two locations with approximately equal reactor volumes between each injection location. The fresh feed is controlled with each injector receiving half of the total fresh feed mass flow. The catalyst components are injected into the polymerization reactor through a specially designed injection stingers. The primary catalyst component feed is computer controlled to maintain the reactor monomer conversion at the specified target. The cocatalyst components are fed based on calculated specified molar ratios to the primary catalyst component Immediately following each reactor feed injection location, the feed streams are mixed with the circulating polymerization reactor contents with static mixing elements. The contents of the reactor are continuously circulated through heat exchangers responsible for removing much of the heat of reaction and with the temperature of the coolant side responsible for maintaining an isothermal reaction environment at the specified temperature. Circulation around the reactor loop is provided by a pump.

The final reactor effluent enters a zone where it is deactivated with the addition of and reaction with a suitable reagent (water). At this same reactor exit location other additives are added for polymer stabilization. For the inventive samples, the conditions were chosen such that at least a 10 fold molar ratio of (hydrate) water vs active catalyst is available to stop the polymerization at the reactor effluent. This aspect is important in order to assure the polymer material has a narrow molecular weight distribution and the composition distribution is maintained narrow.

Following catalyst deactivation and additive addition, the reactor effluent enters a devolatization system where the polymer is removed from the non-polymer stream. The isolated polymer melt is processed and pelletized according to the description provided in WO 2015/191066, pg. 6, 11. 23-28, pg. 8,11. 11-16, and pg. 11, 11. 3-25, which is incorporated herein by reference. The non-polymer stream passes through various pieces of equipment which separate most of the ethylene which is removed from the system. Most of the solvent and unreacted comonomer is recycled back to the reactor after passing through a purification system. A small amount of solvent and comonomer is purged from the process.

TABLE 1 Inv. 1 Inv. 2 Inv. 3 Inv. 4 Inv. 5 Reactor Type Single Single Single Single Single Configuration Comonomer type Type 1-octene 1-octene 1-octene 1-octene 1-octene First Reactor Feed g/g 2.4 2.4 3.1 3.8 3.8 Solvent/Ethylene Mass Flow Ratio First Reactor Feed g/g 0.33 0.34 0.35 0.20 0.22 Comonomer/ Ethylene Mass Flow Ratio First Reactor Feed g/g 9.1E−04 1.0E−03 1.2E−03 3.0E−04 3.6E−04 Hydrogen/ Ethylene Mass Flow Ratio First Reactor ° C. 180 185 195 155 155 Temperature First Reactor barg 41 41 41 34 34 Pressure First Reactor % 94.1 94.5 93.1 86.1 86.2 Ethylene Conversion First Reactor Type CAT-A CAT-A CAT-A CAT-B CAT-B Catalyst Type First Reactor Co- Type CO-CAT-1 CO-CAT-1 CO-CAT-1 CO-CAT-1 CO-CAT-1 Catalyst-1 Type First Reactor Co- Type CO-CAT-2 CO-CAT-2 CO-CAT-2 CO-CAT-2 CO-CAT-2 Catalyst-2 Type First Reactor Co- Ratio 1.2 1.2 1.2 1.2 1.2 Catalyst-1 to Catalyst Molar Ratio (B to Ti or Zr ratio) First Reactor Co- Ratio 10.0 10.0 15.0 5.0 5.0 Catalyst-2 Scavenger Molar Ratio (Al to Ti or Zr ratio) First Reactor min 21.1 20.8 23.9 13.1 12.9 Residence Time

TABLE 2 Description Chemical Name CAT-A dimethyl[[2,2″′-[1,3-propanediylbis(oxy- .kappa.O)]bis[3″,5,5″-tris(1,1-dimethylethyl)- 5′-methyl[1,1′:3′,1″-terphenyl]-2′-olato- .kappa.O]](2-)]-, (OC-6-33)- CAT-B [N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5-.eta.)- 2,3,4,5-tetramethyl-2,4-cyclopentadien-1- yl]silanaminato(2-)-.kappa.N][(1,2,3,4-.eta.)- 1,3-pentadiene]-titanium CO-CAT-1 bis(hydrogenated tallow alkyl)methylammonium tetrakis(pentafluorophenyl)borate(1-) CO-CAT-2 Aluminoxanes, iso-Bu Me, branched, cyclic and linear; modified methyl aluminoxane

Each reaction resulted in the production of a polymer solution containing a low molecular-weight copolymer having the characteristics as described in the Table 3. “NM” refers to values that were not measured.

TABLE 3 Density and Brookfield Viscosity Data Inv. 1 Inv. 2 Inv. 3 Inv. 4 Inv. 5 Comp. 4 Polymer 0.917 0.918 0.917 0.930 0.930 0.933 Density (g/cc) Brookfield 34,008 19,020 10,786 32,544 16,850 73,570 Viscosity (cP)

TABLE 4 Conventional GPC Data Inv. 1 Inv. 2 Inv. 3 Inv. 4 Inv. 5 Comp. 4 M_(n,cc) 12,297 10,713 9,377 10,124 8,554 6,998 M_(w,cc) 24,355 21,032 18,302 22,644 18,877 30,782 M_(z,cc) 38,061 32,684 28,380 37,500 31,142 113,479 M_(w,cc)/M_(n,cc) 2.0 2.0 2.0 2.2 2.2 4.4 M_(z,cc)/M_(n,cc) 3.1 3.1 3.0 3.7 3.6 16.2 w 0.50% 0.20% 0.06% 0.53% 0.17% 4.8% (wt. fraction greater than 10⁵ g/mole)

TABLE 5 Light Scattering GPC Data Inv. 1 Inv. 2 Inv. 3 Inv. 4 Inv. 5 Comp. 4 M_(w,abs) 25,678 20,621 18,164 NM NM 39,160 M_(z,abs) 47,934 35,729 31,287 NM NM 798,722

TABLE 6 DSC Data Inv. 1 Inv. 2 Inv. 3 Inv. 4 Inv. 5 Comp. 4 Tm (° C.) 106.8 108.2 108.1 114.2 113.4 125.3 Tc (° C.) 93.7 93.3 92.9 103.3 102.7 110.3 ΔTm − Tc 13.1 14.9 15.2 10.9 10.7 15.0

TABLE 7 CDBI Data Inv. 1 Inv. 2 Inv. 3 Inv. 4 Inv. 5 Comp. 4 CDBI (%) 86.7 86.5 86.5 78.9 79.3 35.1

Nonwoven Process Conditions (Study #1)

25 gsm, 50 gsm, and 100 gsm monolithic nonwovens are fabricated with a 1 meter Reifenhauser-Reicofil meltblown line at the Nonwovens Institute NWI at the NC State University in Raleigh, N.C., U.S. A single Row Reicofil Cassette having a 0.4 mm hole diameter and 35 holes/inch is used for making the nonwoven fabrics. The total throughput rate is set at 44 kg/hour. The inventive and comparative resins are used to make corresponding inventive and comparative meltblown nonwoven fabrics. For e.g., inventive resin 2 is used to make inventive fabric 2. Additional processing conditions are shown in Table 8.

The SMS composite structure is fabricated as follows: a first bicomponent spunbond nonwoven with basis weight of 20 gsm is inserted as a substrate on the conveyor belt and the meltblown web at basis weight of 4+/−1 gsm is deposited onto the spunbond nonwoven to form a SM structure. Additional processing conditions are shown in Table 8. Using a calendaring process, a second bicomponent spunbond nonwoven having the same composition as the first bicomponent spunbond nonwoven is bonded onto the meltblown side of the SM structure to create a SMS structure (spunbond/meltblown/spunbond). The bonding conditions are at 140° C. and the pressure is 750 psi. The pattern rolls are a diamond pattern with an 18% bond area. The inventive and comparative meltblown nonwoven fabrics are used to make the corresponding inventive and comparative composite structures. For e.g., inventive fabric 2 is used to make inventive composite structure 2. The spunbond nonwovens are formed from bicomponent fibers having a 50% sheath/50% core structure, wherein the sheath comprises 100% polyethylene (e.g., an ASPUN™ fiber grade polyethylene, available from The Dow Chemical Company, Midland, Mich.) and the core comprises 100% polypropylene (e.g., a spunbond fiber grade polypropylene homopolymer).

TABLE 8 Process Conditions for the Manufacture of Monolayer & SMS Meltblown Nonwovens Inven- Compar- Compar- Compar- Compar- tive ative ative ative ative Fabric 2 Fabric 1 Fabric 2 Fabric 3 Fabric 4 Distance 150 150 150 150 150 between conveyor belt to die (mm) Hot air 215 215 215 215 215 temperature (° C.) Hot air flow 325 1100 1100 1100 900 rate (m³/h) Melt 238 230 230 230 238 temperature (° C.) Secondary 30 50 50 50 30 blower fan speed (%) Secondary 25 25 25 25 25 blower air temperature (° C.) Suction fan 40 60 60 60 40 speed (%)

TABLE 9 Tensile & Elongation Data for a 25 gsm Monolayer Meltblown Nonwoven Inven- Compar- Compar- Compar- Compar- tive ative ative ative ative Fabric 2 Fabric 1 Fabric 2 Fabric 3 Fabric 4 MD Peak 0.62 1.70 1.99 2.81 0.61 Tensile Strength (lbf) CD Peak 0.39 1.75 1.41 1.60 0.51 Tensile Strength (lbf) MD 47.2 43.1 24.7 24.9 48.0 Elongation at Break (%) CD 70.7 44.1 40.0 49.5 76.9 Elongation at Break (%)

TABLE 10 Tensile & Elongation Data for a 50 gsm Monolayer Meltblown Nonwoven Inven- Compar- Compar- Compar- Compar- tive ative ative ative ative Fabric 2 Fabric 1 Fabric 2 Fabric 3 Fabric 4 MD Peak 0.95 5.95 5.25 3.25 1.30 Tensile Strength (lbf) CD Peak 0.78 4.00 3.20 5.91 1.07 Tensile Strength (lbf) MD 38.4 16.9 14.4 42.6 52.9 Elongation at Break (%) CD 57.2 18.3 30.3 25.3 74.5 Elongation at Break (%)

TABLE 11 Tensile & Elongation Data for a 100 gsm Monolayer Meltblown Nonwoven Inven- Compar- Compar- Compar- Compar- tive ative ative ative ative Fabric 2 Fabric 1 Fabric 2 Fabric 3 Fabric 4 MD Peak 1.62 12.51 10.82 11.08 2.77 Tensile Strength (lbf) CD Peak 2.47 8.89 6.51 5.48 2.21 Tensile Strength (lbf) MD 47.7 9.5 14.5 9.8 43.2 Elongation at Break (%) CD 30.2 12.0 25.7 30.4 68.3 Elongation at Break (%)

TABLE 12 Tensile & Elongation Data for SMS Composite Structure Using a 4 +/− 1 gsm Monolayer Meltblown Nonwoven Inven- Compar- Compar- Compar- tive ative Compar- ative ative Com- Com- ative Com- Com- posite 2 posite 1 Composite 2 posite 3 posite 4 MD Peak 11.81 NM 8.16 NM 10.96 Tensile Strength (lbf) CD Peak 3.56 NM 1.60 NM 2.72 Tensile Strength (lbf) MD 108.7 NM 50.0 NM 95.4 Elongation at Break (%) CD 174.6 NM 89.4 NM 134.4 Elongation at Break (%)

Referring to Table 12, the inventive composite structure is a spunbond-meltblown-spunbond (SMS) composite structure formed using Inventive Fabric 2 for the meltblown nonwoven layer. The comparative composite structures are also SMS composite structures formed using corresponding Comparative Fabrics 2 and 4 in the meltblown nonwoven layer. As shown in Table 12, the inventive composite structure shows improvement in both peak tensile strength and elongation at break in comparison to the comparative composite structures.

TABLE 13 Air Permeability of Monolayer Meltblown Nonwovens Inv. Comp. Comp. Comp. Comp. Fabric 2 Fabric 1 Fabric 2 Fabric 3 Fabric 4 Air Permeability for 127 149 125 70 381 25 gsm Meltblown Nonwoven (cubic feet per minute) Air Permeability for 87 22 57 29 111 50 gsm Meltblown Nonwoven (cubic feet per minute) Air Permeability for 33 7.5 16 15 60 100 gsm Meltblown Nonwoven (cubic feet per minute)

Referring to Table 13, the inventive nonwoven fabric shows improvement in air permeability over comparative fabric 4, which is ethylene-based.

TABLE 14 Hydrohead Failure Pressure of Monolayer Meltblown Nonwovens Inven- Compar- Compar- Compar- Compar- tive ative ative ative ative Fabric 2 Fabric 1 Fabric 2 Fabric 3 Fabric 4 Hydrohead 19 29 29 50 17 Failure Pressure for 25 gsm Meltblown Nonwoven (mbar) Hydrohead 29 44 53 76 28 Failure Pressure for 50 gsm Meltblown Nonwoven (mbar) Hydrohead 45 88 77 88 31 Failure Pressure for 100 gsm Meltblown Nonwoven (mbar)

Referring to Table 14, the inventive nonwoven fabric saw improvement in hydrohead failure pressure over comparative fabric 4, which is ethylene-based.

TABLE 15 Hand Feel of Monolayer Meltblown Nonwovens (50 gsm) Inven- Compar- Compar- Compar- Compar- tive ative ative ative ative Fabric 2 Fabric 1 Fabric 2 Fabric 3 Fabric 4 Hand Feel for 22 NM 173 NM 37 50 gsm Meltblown Nonwoven (g)

Referring to Table 15, the inventive nonwoven fabric shows significant improvement in hand feel over the comparative polypropylene-based fabric (comp. fabric 2), but also shows improvement in hand feel over comparative fabric 4, which is ethylene-based.

Nonwoven Process Conditions (Study #2)

50 gsm monolithic nonwovens are fabricated with a 1 meter Reifenhauser-Reicofil meltblown line at the Nonwovens Institute NWI at the NC State University in Raleigh, N.C., U.S. A single Row Reicofil Cassette having a 0.4 mm hole diameter and 35 holes/inch is used for making the nonwoven fabrics. The total throughput rate is set at 44 kg/hour. The inventive and comparative resins, as described in Study 1 above, are used to make corresponding inventive and comparative meltblown nonwoven fabrics. For e.g., inventive resin 4 is used to make inventive fabric 4. Additional processing conditions are shown in Table 16.

The SMS composite structure is fabricated as follows: a first bicomponent spunbond nonwoven with a basis weight of 20 gsm is inserted as a substrate on the conveyor belt and the meltblown web at a basis weight of 4 +/−1 gsm is deposited onto the spunbond nonwoven to form a SM structure. Additional processing conditions are described in Table 17. Using a calendaring process, a second bicomponent spunbond nonwoven having the same composition as the first bicomponent spunbond nonwoven is bonded onto the meltblown side of the SM structure to create a SMS structure (spunbond/meltblown/spunbond). The bonding conditions are at 130° C. and the pressure is 750 psi. The pattern rolls are a diamond pattern with an 18% bond area. The inventive and comparative meltblown nonwoven fabrics are used to make the corresponding inventive and comparative composite structures. For e.g., inventive fabric 4 is used to make inventive composite structure 4. The spunbond nonwovens are formed from bicomponent fibers having a 50% sheath/50% core structure, wherein the sheath comprises 100% polyethylene (e.g., an ASPUN™ fiber grade polyethylene, available from The Dow Chemical Company, Midland, Mich.) and the core comprises 100% polypropylene (e.g., a spunbond fiber grade polypropylene homopolymer).

TABLE 16 Process Conditions for the Manufacture of Monolayer Meltblown Nonwovens Inventive Inventive Inventive Inventive Comparative Comparative Fabric 1 Fabric 3 Fabric 4 Fabric 5 Fabric 2 Fabric 4 Distance 150 150 150 150 150 150 between conveyor belt to die (mm) Hot air 215 215 215 215 215 215 temperature (° C.) Hot air flow 500 500 500 500 500 500 rate (m³/h) Melt 231 231 231 231 231 231 temperature (° C.) Secondary 30 30 30 30 30 30 blower fan speed (%) Secondary 25 25 25 25 25 25 blower air temperature (° C.) Suction fan 60 60 60 60 60 60 speed (%)

TABLE 17 Process Conditions for the Manufacture of an SMS (Spunbond/Meltblown/Spunbond) Composite Inventive Inventive Inventive Inventive Comparative Comparative Composite 1 Composite 3 Composite 4 Composite 5 Composite 2 Composite 4 Distance 150 150 150 150 150 150 between conveyor belt to die (mm) Hot air 215 215 215 215 215 215 temperature (° C.) Hot air flow 500 500 500 500 1000 500 rate (m³/h) Melt 231 231 231 231 231 231 temperature (° C.) Secondary 30 30 30 30 30 30 blower fan speed (%) Secondary 25 25 25 25 25 25 blower air temperature (° C.) Suction fan 60 60 60 60 60 60 speed (%)

TABLE 18 Tensile & Elongation Data for SMS Composite Structure Using a 4 +/− 1 gsm Monolayer Meltblown Nonwoven Inventive Comparative Composite 5 Composite 2 MD Tensile Strength (lbf) 13.5 13.3 CD Tensile Strength (lbf) 7.1 6.4 MD Elongation at Break (%) 39.8 39.0 CD Elongation at Break (%) 75.1 64.8

Referring to Table 18, the inventive composite structure is a spunbond-meltblown-spunbond (SMS) composite structure formed using Inventive Fabric 5 for the meltblown nonwoven layer. The comparative composite structure is also an SMS composite structures formed using corresponding Comparative Fabric 2 in the meltblown nonwoven layer as previously described in the first study. As shown in Table 18, the inventive composite structure shows improvement in both peak tensile strength and elongation at break in comparison to the comparative composite structure.

TABLE 19 Air Permeability of a Monolayer Meltblown Nonwoven Inventive Inventive Inventive Inventive Comparative Comparative Fabric 1 Fabric 3 Fabric 4 Fabric 5 Fabric 2 Fabric 4 Air 119 67 106 68 115 301 Permeability for 50 gsm Meltblown Nonwoven (cubic feet per minute)

Referring to Table 19, the inventive nonwoven fabrics show improvement in air permeability over comparative fabric 4, which is ethylene-based, and the inventive nonwoven fabrics also show comparable performance or improvement in air permeability over comparative fabric 2, which is propylene-based.

TABLE 20 Hydrohead Failure Pressure (ISO) of a Monolayer Meltblown Nonwoven Inventive Inventive Inventive Inventive Comparative Comparative Fabric 1 Fabric 3 Fabric 4 Fabric 5 Fabric 2 Fabric 4 Hydrohead 23.5 26.8 32.5 40.9 24.9 14.6 Failure Pressure for 50 gsm Meltblown Nonwoven (mbar)

Referring to Table 20, the inventive nonwoven fabrics exhibit improvement in hydrohead failure pressure (ISO) over comparative fabric 4, which is ethylene-based. Also, the inventive nonwoven fabrics exhibit comparable or improvement in hydrohead failure pressure (ISO) over comparative fabric 2, which is propylene-based.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm ”

Every document cited herein, if any, including any cross-referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention. 

We claim:
 1. An ethylene/alpha-olefin interpolymer suitable for use in fibers and nonwovens having a density of from 0.911 to 0.939 g/cc, a Brookfield viscosity of less than or equal to 50,000 cP, and a molecular weight distribution (M_(w,cc)/M_(n,cc)) of 1.8 to 3.5, and an M_(zcc)/M_(ncc) is less than 5.25.
 2. The interpolymer of claim 1, wherein the ethylene/alpha-olefin interpolymer has a weight fraction (w) of molecular weight greater than 10⁵ g/mole, based on the total weight of interpolymer, as determined by conventional gel permeation chromatography, of less than 2.5%.
 3. The interpolymer of claim 1, wherein the ethylene/alpha-olefin interpolymer has a comonomer distribution breadth index of greater than 50%, or alternatively, from 50% to 98%, or alternatively, 50% to 85%.
 4. A meltblown nonwoven comprising an ethylene/alpha-olefin interpolymer, wherein the ethylene/alpha-olefin interpolymer has: a density of from 0.911 to 0.939 g/cc, a Brookfield viscosity of less than or equal to 50,000 cP, and a molecular weight distribution (M_(w,cc)/M_(n,cc)) of 1.8 to 3.5, and an M_(zcc)/M_(ncc) of less than 5.25, or alternatively, less than 4.0 or 3.5.
 5. The meltblown nonwoven of claim 4, wherein the ethylene/alpha-olefin interpolymer has a weight fraction (w) of molecular weight greater than 10⁵ g/mole, based on the total weight of interpolymer, and as determined by conventional gel permeation chromatography, of less than 2.5%.
 6. The meltblown nonwoven of claim 4, wherein the ethylene/alpha-olefin interpolymer has a comonomer distribution breadth index of greater than 0%.
 7. A composite structure comprising the meltblown nonwoven of claim
 4. 8. The composite structure of claim 7, wherein the composite structure further comprises one or more spunbond nonwovens.
 9. A composite structure having a S_(a)M_(b)S_(c) configuration, wherein S is a spunbond nonwoven, M is the meltblown nonwoven of 4, and a, b, and c are the number of layers and are independent integers ranging from 1 to
 5. 10. The composite structure of claim 9, wherein the spunbond nonwoven is formed from bicomponent fibers having a sheath/core structure, wherein the sheath comprises polyethylene and the core comprises polypropylene.
 11. The composite structure of claim 9, wherein the spunbond nonwoven is formed from monocomponent fibers, wherein the monocomponent fibers comprise polyethylene. 